Method of rendering textiles flame retardant with phosphorus containing melamine

ABSTRACT

New compounds are disclosed of the formula   WHEREIN R is independently selected from the group consisting of   AND WHEREIN R&#39;&#39; is lower alkyl. The compounds of this invention serve as flame retarding agents for textiles and as additives to render polymers and copolymers flame retardant.

United States Patent 91 Golborn et al.

[451 May 27, 1975 METHOD OF RENDERING TEXTILES FLAME RETARDANT WITHPHOSPHORUS CONTAINING MELAMINE [75] Inventors: Peter Golborn, Lewiston;James J.

Duffy, Buffalo, both of NY.

[73] Assignee: Hooker Chemicals & Plastics Corp., Niagara Falls, NY.

221 Filed: Sept. 28, 1973 21 Appl. No.: 401,767

Related U.S. Application Data [62] Division of Ser. No. 239,797, March30, 1972,

Primary Examiner-Stephen J. Lechert, Jr. Attorney, Agent, or Firm-PeterF. Casella; Donald C. Studley; William .1. Crossetta, Jr.

[57] ABSTRACT New compounds are disclosed of the formula RCH when NewNYN NHCHZR wherein R is independently selected from the group consistingof and wherein R is lower alkyl. The compounds of this invention serveas flame retarding agents for textiles and as additives to renderpolymers and copolymers flame retardant.

16 Claims, No Drawings METHOD OF RENDERING TEXTILES FLAME RETARDANT WITHPHOSPHORUS CONTAINING MELAMINE This is a division of application Ser.No. 239,797, filed Mar. 30, 1972, now abandoned.

FIELD OF INVENTION This invention relates to novel compounds of theformula N Rcn HN NHCH R II NHCHZPIOR' wherein R is independentlyselected from the group consisting of BACKGROUND OF THE INVENTION Manyflame retarding agents and methods of application have been developed inattempts to obtain flame resistant textile materials and thermoplasticand thermosetting resin compositions.

Flame retardant textiles have been produced by depositing metal oxides,within or on the textile fibers, by the successive precipitation offerric oxides and a mixture of tungstic acid and stannic oxide or bysuccessive deposition of antimony trioxide and titanium dioxide. Suchprocesses require plural treatment baths in which strongly acidicsolutions are employed thus posing the problem of possible textiledegradation. Furthermore, metal oxide coatings on textile materialscreate difficulties in subsequent dyeing processes which deleteriouslyaffect the hand of the finished product. Another process involves theuse of a single processing bath wherein a dispersion of a chlorinatedhydrocarbon and finely divided antimony oxide is padded on the textilematerial. Near the textile combustion temperature antimony oxide willreact with hydrogen chloride. generated by degradation of thechlorinated hydrocarbon, to form antimony oxychloride which acts tosuppress flame. This combination of a chlorinated hydrocarbon and finelydivided antimony oxide are not acceptable finishes for closely woventextiles as they deleteriously affect the hand of the finished product.A further process for imparting flame resistance to cellulosic materialsis by the esterification of the cellulose with diammonium hydrogenorthophosphate. Textile products so treated however are subjected tometathesis reaction with cations during washing, and must be regeneratedby reacting the wash product with an ammonium chloride solution.

The production of thermoplastic and thermosetting resin compositionswhich are flame retardant is of considerable commercial importance. Forexample, such articles as castings, moldings, foamed 0r laminatedstructures and the like are required, or are at least desired, to beresistant to fire and flame and to possess the ability to endure heatwithout deterioration. The use of various materials incorporated intothermoplastic and thermosetting resins so as to improve the flameretardance thereof has ben known. Many compounds have been commerciallyavailable for such use, among them being chlorostyrene copolymers,chlorinated paraffin wax in admixture with triphenyl styrene,chlorinated paraffins and aliphatic antimonical compounds, as well asantimony oxide-chlorinated hydrocarbon mixtures. A problem associatedwith these compounds has been however, the fact that generally a largeamount, i.e. up-

wards of 35 percent of additive, must be incorporated into the resin inorder to make it sufficiently flame retardant. Such large amounts ofadditive may deliteriously affect the physical characteristics of thethermoplastic resin, as well as substantially complicating andincreasing the cost of preparation thereof. A further problem is thatthese prior art additives tend to crystallize or oil out of the resinafter a relatively short time of incorporation. The present inventionrelates to a group of compounds which may be added to thermoplastic andthermosetting resins in relatively small amounts and still producesatisfactory flame retardant compositions which will not crystallize noroil out of the resin after incorporation therein.

OBJECTS OF THE INVENTION It is, therefore, a principal object of thisinvention to provide novel compounds of the formula:

0 RcH -HN L HCH R consisting of mi and (R' oi and wherein R is loweralkyl.

It is also an object of this invention to provide flame retardingtextile materials comprising normally flammable cellulosic,proteinaceous or analogous manmade materials. Another object is toprovide a method for treating normally flammable cellulosic,proteinaceous or analogous man-made materials to render them flameretardant. Another object is to provide flame retarding thermoplasticand thermosetting resin compositions comprising normally flammablethermoplastic and thermosetting resin materials. A further object is toprovide a process for treating normally flammable thermoplastic andthermosetting resin compositions to render them flame retardant. Aparticular object is to devise a composition comprising normallyflammable cellulosic, proteinaceous or analogous manmade materials andan effective flame retardant amount of the compound represented by theformula RCHZHN N uucu pma' NHCH. R

DESCRIPTION OF THE INVENTION In accordance with this invention there areprovided novel compounds, for imparting flame retardancy to textiles andthermoplastic and thermosetting resin materials, of the formula 0 N\ nRCH -NH I 2 f NHCHZNOR NHCH R wherein R is independently selected fromthe group consisting of N H HO-CH -NH "f Wl"'NHCH -P(OCH CH CH CH CH Thesynthesis of the compositions of the present invention is accomplishedby reacting a N- hydroxymethylated melamine of the formula NHCH OH witha trialkyl phosphite of the formula (R'O) P R is as previously describedin a suitable solvent, excess phosphite or neat Typically, the reactionoccurs at elevated temperatures and is continued for about 1 to about 12hours. Temperatures are generally about 50 to about 160C. Preferablyreaction is continued from about 3 to about 6 hours at a temperature ofabout to about C. The solvent and other volatiles are thereafterstripped, or otherwise removed from the product. Suitable solventsinclude alcohols, glymes, dimethyl formamide or mixtures of the previoussolvents with aliphatic or aromatic hydrocarbons.

One or more of the novel compounds of this invention may be applied totextile materials by conventional finishing techniques such as bythermal induced pad curing so as to incorporate into the textile a flameretardant amount thereof. The compounds of this invention haveadvantages over the flame retardant agents of the prior art in that theymay be used on a variety of textile materials of different chemicalcomposition, and they may be applied by a variety of methods. They maybe applied to materials in either the fiber or fabric form to give flameretarding materials with minimum detectable physical changes in thequality or hand of the textile material.

The products of this invention may be applied to cellulosic materials inseveral ways to give a durable flame retardant treatment. For example,the products of this invention may be reacted with formaldehyde to giveN- hydroxymethyl derivatives which can react with cellulosic materialsin a known manner. Alternatively aqueous mixtures of the products withformaldehyde, urea, trimethylol melamine or other known cellulosecrosslinking agents may be applied to a cellulose substrate with the aidof an acidic catalyst by a pad dry process. A further method is to mixthe invention with an acid catalyst in aqueous solution and applydirectly.

More preferably the Nhydroxymethyl derivative of the products of thisinvention prepared by the condensation of the products withformaldehyde, are mixed in an aqueous medium with trimethylol malamineand a Lewis acid catalyst such as NH Cl or Zn(NO -6H O. The cellulosicmaterial is immersed in an aqueous solution of the methylol derivative,trimethylol melamine, and Zn(NO -6H O and squeezed on a two roll padderto 7090% wet weight pick-up. The material is dried at 220270F for 1-3minutes and cured at 300370F for l6 minutes in a circulating air oven.The samples are then washed in hot water and dried. The finished sampleshave a flame retardant add-on of about 5 to about 40 percent andpreferably about 10 to about 25% by weight.

The flame retardant agents of this invention may be applied to varioustextiles such as cellulosic material, proteinaceous materials and blendsof cellulosic or proteinaceous materials and analogous man-made fibers.By cellulosic materials, applicant intends to embrace cotton, rayon,paper, regenerated cellulose and cellulose derivatives which retain acellulose backbone of at least one hydroxy substituent per repeatingglucose unit. By proteinaceous material applicant intends to embracethose textile materials comprising the functional groups of proteinssuch as the various animal wools, hairs and furs.

The flame retardant compounds or additives of the invention may beincorporated into thermoplastic or thermosetting resin compositions byany known method. That is to say, the flame retardant additive may beadded to the resin by milling the resin and the additive on, forexample, a two-roll mill, or in a Banbury mixer etc., or it may be addedby molding or extruding the additive and resin simultaneously, or bymerely blending it with the resin in powder form and thereafter formingthe desired article. Additionally, the flame-retardant may be addedduring the resin manufacture, i.e., during the polymerization procedureby which the resin is made, provided the catalysts etc. and otheringredients of the polymerization system are inert thereto. Generally,the compounds of this invention may be incorporated into thethermoplastic and thermosetting resin in flame-retarding amounts, i.e.generally amounts ranging from about 5 percent by weight, to about 50percent by weight, preferably from about percent by weight, to about 40percent by weight, based on the weight of the polymer, have been foundsufficient.

The thermoplastic and thermosetting resins embraced within the scope ofthis invention include the homopolymers and copolymers of unsaturatedaliphatic, alicyclic, and aromatic hydrocarbons. Suitable monomers areethylene, propylene, butene, pentene, hexane, heptene, octene,2-methylpropene-l, 3- methylbutenel, 4-methylpentene-l ,4-methyl-hexene-1,5-methylhexenel bicyclo-( 2.2.1 )-2-heptene, butadiene, pentadiene,hexadiene, isoprene, 2,3-dimethylbutadiene-1,3 2-methylpentadienel ,3,4- vinylcyclohexene, vinylcyclohexene, cyclopentadiene, styrene andmethylstyrene, and the like.

Other polymers in addition to the above-described olefin polymers thatare useful in the invention include polyindene, idenecoumarone resins;polymers of acrylate esters and polymers of methacrylate esters,acrylate and methacrylate resins such as ethyl acrylate, nbutylmethacrylate, isobutyl methacrylate, ethyl methacrylate and methylmethacrylate; alkyd resins and paint vehicles, such as bodied linseedoil; cellulose derivatives such as cellulose acetate, cellulose acetatebutyrate, cellulose nitrate, ethyl cellulose, hydroxyethyl cellulose,methyl cellulose and sodium carboxymethyl cellulose; epoxy resins; furanresins (furfuryl alcohol or furfuralketone); hydrocarbon resins frompetroleum; isobutylene resins (polyisobutylene); isocyanate resins(polyurethanes); melamine resins such as melamineformaldehyde andmelamine-urea-formaldehyde; oleoresins; phenolic resins such asphenol-formaldehyde, phenolic-elastomer, phenolic-epoxy,phenolicpolyamide, and phenolic-vinyl acetals; polyamide polymers, suchas polyamides, polyamide-epoxy and particularly long chain syntheticpolymeric amides containing recurring carbonamide groups as an integralpart of the main polymer chain; polyester resins such as unsaturatedpolyesters of dibasic acids and dihydroxy compounds, and polyesterelastomer and resorcinol resins such as resorcinolformaldehyde,resorcinol-furfural, resorcinol-phenol-formaldehyde,resorcinol-polyamide and resorcinol-urea; rubbers such as naturalrubber, synthetic polyisoprene, reclaimed rubber, chlorinated rubber,polybutadiene, cyclized rubber, butadiene acrylonitrile rubber,butadiene-styrene rubber, and butyl rubber; neoprene rubber(polychloroprene); polysulfides (Thiokol); terpene resins; urea resins;vinyl resins such as polymers of vinyl acetal, vinyl acetate or vinylalcohol-acetate copolymer, vinyl alcohol. vinyl chloride, vinyl butyral,vinyl chloride-acetate copolymer, vinyl pyrrolidone and vinylidenechloride copolymers; polyformaldehyde; polyphenylene oxide; polymers ofdiallyl phthalates and phthalates; polycarbonates of phosgene orthiophosgene and dihydroxy compounds such as bisphenols, phosgene,thermoplastic polymers of bisphenols and epichlorohydrin (trade namedPhenoxy polymers); graft copolymers and polymers of unsaturatedhydrocarbons and unsaturated monomer, such as graft copolymers ofpolybutadiene, styrene and acrylonitrile, commonly called ABS resins;ABS polyvinyl chloride polymers, recently introduced under the tradename of Cycovin; and acrylic polyvinyl chloride polymers, known by thetrade name Kydex 100.

The polymers of the invention can be in various physical forms, such asshaped articles, for example, moldings, sheets, rods, and the like;fibers, coatings, films and fabrics, and the like.

The compounds of this invention have been found to have particularutility in ABS resins and in elastomeric materials such as acrylicrubber; acrylonitrilebutadiene styrene terpolymers;butadieneacrylonitrile copolymers; butyl rubber; chlorinated rubbers,e.g., polyvinyl chloride resins, chloroprene rubber, chlorosulfonatedpolyethylene; ethylene polymers, e.g., ethylene-propylene copolymers,ethylene-propylene terpolymers; fluorinated rubbers, butadiene rubbers,e.g., styrene-butadiene rubber, isobutylene polymers, polybutadienepolymers, polyisobutylene rubbers, polyisoprene rubbers; polysulfiderubbers; silicon rubbers; urethane rubbers; high styrene resins latices,high styrene resins, vinyl resins; sponge rubber; and the like.

It should be noted that it is also within the scope of the presentinvention to incorporate such ingredients as plasticizers, dyes,pigments, stabilizers, antioxidants, antistatic agents and the like tothe novel composition.

ASTM Test D2863-70, used in accordance with the following examples,generally provides for the comparison of relative flammability ofself-supporting plastics by measuring the minimum concentration ofoxygen in a slowly rising mixture of oxygen and nitrogen that willsupport combustion. The procedure encompasses supporting cylindricaltest specimens -150 mm X 8.0 mm vertically in a glass tube fitted withcontrolled upward oxygen/nitrogen gas flow. The top of the specimen isignited and oxygen flow is adjusted until it reaches that minimum ratewhich the specimen is extinguished before burning 3 minutes or 50 mmwhichever happens first. The oxygen index(n) is then calculated asfollows:

wherein O is the volumetric flow of oxygen, at the minimal rate and N isthe corresponding volumetric flow rate of nitrogen.

A modification of ASTM Test D635-68 used in accordance with thefollowing examples, generally provides for the comparison of burningrates, selfextinguishment and non-burning characteristics of plastics inthe form of sheets, bars, plates or panels. The procedure encompassespreparing 150-200 mm X 8 mm plastic samples with and without the subjectflame retardant additive. Each sample is marked at points 1 inch and 4inches from its end and held, marked end in the flame, at a 45 angle ina controlled burner flame (1 inch flame length) for two 30 secondattempt. The movement of the flame up the length of the sample throughthe two points is measured for rate of burning, non-burning orself-extinguishing characteristics. A sample is ratedSE(self-extinguishing) if the flame burns through the first point butextinguishes before reaching the second point. A sample is ratedNB(nonburning) if, upon ignition it does not burn to the first point.

AATCC test method 34-1969, The Vertical Char Test, used in accordancewith the following examples, generally provides for the comparison ofrelative flammability of 2% inch X 10 inch fabric test specimens whenexposed to a controlled burner flame, under controlled conditions, forperiods of 12.0 and 3.0 seconds. Charred specimens are thereaftersubjected to controlled tearing tests, using tabulated weights, todetermine the average tear length as representing the char length of thefabric. In addition, samples which are wholly consumed by the flame arerated (B) and samples which do not burn are rated (NB). For comparisonpurposes, it should be noted that untreated samples of the fabrics usedin the examples of this case would be consumed for this test.

In all the examples of the application, the following general procedurewas used except when otherwise specifically noted. Padding was done on astandard two roll laboratory padder at a gauge pressure of about 60pounds per square inch in all cases. Drying and curing during processingwere done with a standard laboratory textile circulating air oven.Washing and drying was done in a standard, home, top loading, automaticwasher and dryer. A Hooker Boil (HE) is done in a standard, center post,wringer washer fitted with internal steam coils. The sample to betreated is washed and agitated therein for 45 minutes in a solutioncontaining 88 pounds of water, 100 grams of sodium carbonate, 100 gramsoflvory" soap and 10 grams ofTide" detergent at a temperature of about200 to about 210 Fahrenheit. The washer is then drained, the samplesqueezed through the wringer and again washed and agitated therein forminutes in about 88 pounds of water at about 140 to about 160Fahrenheit.

The following examples are set forth for purposes of illustration onlyand are not to be construed as limitations of the present inventionexcept as set forth in the appended claims. All parts and percentagesare by weight unless otherwise specified.

EXAMPLE I Preparation of ll HOCH NH /N 2 written H001 NHCH OH 216g. oftrimethylol melamine (1.0 mole) was dissolved in 1 liter ofN,N-dimethylforamide, using a 2 liter, round bottom, three necked flask,fitted with mechanical stirrer, thermometer, and condenser with a takeoff. The mixture was then heated to and maintained at l 10C. while 124g.of trimethylphosphite was slowly dropped into the reaction mixture overa period of 1.5 hours. Methanol was recovered from the condenser takeoff during the course of the reaction. After the addition was completethe mixture was heated for an additional one half hour at 115120C andthe solvent was then removed on a rotary evaporator, at C under 2 mm Hg,to give the desired product in quantitative yield.

Infrared, nuclear magnetic resonance and elemental analyses showed theproduct to be essentially pure.

EXAMPLE II Preparation of H (ocH cH A mixture of 0.5 mole oftriethylphosphite and 0.5 liter of diglyme was heated to 120 in a threenecked, round bottom, flask with thermometer, stirrer, and condenser. Tothis mixture was added 0.25 mole of trimethylomelamine in small portionsover 0.5 hour time period. After the addition was complete, the mixturewas stirred for 1 hour and the solvent and other volatiles were thenremoved on a rotary evaporator, at 80C and 2 mm Hg. The resulting clearviscous liquid, when tested by elemental, infrared and nuclear magneticresonance spectroscopy, analysis was shown to be essentially puredesired product.

EXAMPLE III Preparation of NHCH P(OCl-l Trimethylol melamine (54g, 0.25mole) was mixed with trimethyl phosphite (496g, 4.0 mole) in a 1 liter,round bottom, three necked flask fitted with a mechanical stirrer,condenser and thermometer. The mixture was slowly warmed to about 1 10Cand distillate, identified as methanol diluted with a small amount oftrimethyl phosphite, was continuously collected in the take off. Heatingwas continued until the distillate subsided and thereafter for oneadditional hour at C. Excess phosphite was then removed by a rotaryevaporator, under reduced pressure at 80C, yield; the desired product, aclear colorless liquid. The desired product was found to be essentiallypure by infrared and nuclear magnetic resonance analyses.

EXAMPLE IV In the first stage 5.0 oz. sq. yd. of cotton fabric waspadded with an aqueous solution containing 40 parts of Bis (N-dimethylphosphonomethyl) N-hydroxymethyl melamine, 50 parts of water and partsof Zn(NO '6- H O.

The fabric was then squeezed to 80 percent wet pickup on a laboratorypadder, dried for about 2 minutes at about 250F and cured for about 4minutes at about 350F in a circulating air oven. The fabric was thenwashed with tide detergent, for one wash cycle in a standard, home type,automatic washer and tumble dried. The thus treated and washed fabricwas found to have an initial resin add-on of about 16.2 percent and whentested by AATCC method 34-1969, had an initial calculated char length of5.5 inches.

In the second stage the thus treated and washed fabric was subjected to4 more cycles (total=5 and when tested by AATCC method 34-1969, had acalculated char length of 6.1 inches. Data, pertaining to Example 4 hasbeen tabulated in Table 1 for comparison.

EXAMPLE VIX 5 oz. per square yard of cotton fabric was padded, with anaqueous solution containing the components as described in Table l, andthereafter treated and tested in accordance with the first stageprocedure of Example IV. Thereafter, samples were individually subjectedto 4 additional wash cycles (total=5), 14 additional washes (total 15),one Hooker boil (as above described) or three Hooker boils. Each of theindividually subjected samples were then tested by AATCC method 34-1969and char length calculated therefore. Data, pertaining to Examples V-IX,has been tabulated in Table l for comparison.

TABLE EXAMPLE x grams of tris-N-diethylphosphone0methyl melamine wasdissolved in 100 ml of 40 percent formalin solution and stirred at C forthree hours at a pH of 9.5-10.0. The mixture was cooled to roomtemperature and the pH adjusted to 7.0 with hydrochloric acid.

5.0 02. sq. yd. cotton fabric was padded through this solution andsqueezed on a two roll laboratory padder to about 85 percent wet pickup.The fabric was then dried at about 250F for about 2 minutes and cured atabout 330F for about 5 minutes in a circulating air oven. The fabric wasthen washed with tide detergent for one wash cycle in a standard hometype, automatic washer. and tumble dried. The thus treated fabric wasfound to have an initial resin add-on of about 20.2 percent and whentested by AATCC method 34-1969 had an initial char length of 4.3 inches.The thus treated and washed fabric was subjected to 9 more wash cyclesand, when tested by AATCC method 34-1969 had a calculated char length of5.0 inches.

EXAMPLE Xl A padding solution was prepared by the process of Example Xutilizing tris-Ndimethylphosphonomethyl melamine. 5.0 ounce per squareyard cotton fabric was padded through this above solution and thereaftertreated and tested in accordance with Example X. The results of testingindicated an initial vertical char of 3.8 inches with a 4.9 inchvertical char after 10 wash cy cles.

EXAMPLE Xll A solution was prepared, as in Example X, to which was added25g of a 50 percent methylolated melamine solution and 7.5g of Zn(NO '6HO.

5.0 oz. cotton fabric was immersed in this solution 40 and squeezed on atwo roll laboratory padder to 85 per- Trimethylol VerticaT Char (inzhs)H 0 Zn(NO CH 0 Urea Melamine Percent Fzer After Arter- Fiame Retardant Prts by Pa i b Pans b Parts by Resin 1 Home 5 Home 15 Ham 1 3 Examph 50Parts by Weight Hei ht Height Weight Height Add-on Hash Hashes dashes H8H3 0 (cm 1 H HN NHCH -P 11! Hot 2 I 2 3 2 5 16.1 5.5 6.1

1111c11 -Pu1c11 V ditto $0 5 5 13.8 5.1 3.9 3.8 7.9 8.

VI ditto I0 S 15 26.1 3.8 5.8 3.1 3.1 5.7

N m llmc"ZM'I/ WHNCHZDH s5 5 17.9 5.1 4.1 7.1 8.8 7.1

N\ N o NHCH -P(OCH3) 'vm ditto so 5 5 1 .1 11.2 7.1 u.9 7.1

U1 ditto IO S 15 28.2 2.7 5.2 6-1 5.2, 4.8

cent wet pickup. The fabric was then dried at about 240F for about 2.5minutes and cured at about 330F for about minutes in a circulating airoven. The fabric was washed, with tide detergent in a standard home typeautomatic washer for one complete wash cycle and tumble dried. The thustreated fabric was subjected to testing by AATCC method 34-1969 and hada calculated char length of 4.2 inches. The treated and washed fabricwas thereafter subjected to nine more wash cycles and, when tested byAATCC method 34-1969 had a calculated char length of 5.1 inches.

EXAMPLES XIIIXV Solutions were prepared at 5 ounces per square yardcotton fabric treated and tested by the procedure of Example '12 usingthe phosphorus containing melamine derivatives denoted in Table II. Theresults of testing are as indicated therein.

EXAMPLE XVI 8 oz. per sq. yd. Bedford wool cord was padded with anaqueous solution containing 20 parts of N-dimethylphosphonomethyl-bis-hydroxymethyl melamine, 5 parts of Zn(NO'6I-I O and 75 parts of water.

The fabric was squeezed to about 65 percent wet pick-up on a laboratorypadder and cured for about 4 minutes at 350F in a circulating air oven.The fabric was then washed by rinsing with water for about 10 minutesand thereafter air dried. Resin add on was calculated to be about 10.7percent by weight. This fabric was then subjected to testing under AATCCtest method 34-1969 and had a calculated char length of 2.3 inches. Thefabric was then subjected to four additional water wash cycles andtested by AATC test method 34-1969 to have a 2.5 inch char length.

EXAMPLE xvn grams of tris-N-dimethylphosphonomethyl melamine wasdissolved in 40 percent formalin solution (g) and stirred over nightatpH 10. The pH was adjusted to 7.0 with hydrochloric acid and 5g ofammonium chloride and thereafter 23 g of a 50 percent solution oftrimethylol melamine was added. 6.0 oz. per square yard wool fabric waspadded through the solution and squeezed to about percent wet pick-up.The fabric was dried at about 250F for about 2 minutes and cured forabout 5 minutes at about 350F in a circulating air oven. The fabric waswashed by hand for about 5 minutes in a water-detergent (tide) mixtureand tumbled dried. Resin add on was calculated to be 29 percent. Thefabric was then subjected to AATCC test method 34-1969 and had acalculated char length of 3.3 inches. The fabric was then subjected to 4additional wash and dry cycles as above described and when subjected totesting had a char length of 3.5 inches.

EXAMPLE XVIII Rayon staple fiber was immersed in the padding solution ofExample XVII, and thereafter squeezed on a laboratory padder to percentwet pick-up. The fiber was then dried in a circulating air oven at about250F for about 5 minutes and cured at about 350F for about 10 minutes.The fabric was then washed by hand in running water for about 5 minutesand air dried. Untreated rayon staple fiber and the treated fiber weretested when ASTM test D2863-70 and found to have an oxygen index of 18.9and 29.0 respectively. Both the untreated and treated rayon fiber wereplaced in a burner flame for 3 seconds. The untreated fiber was 'r A a Le n Verucnl Cha (inches) Examplg Compound lnirial After l0 Hash CyzleS oo N a 5.\ XII tocu cuy vcn nnf/ m nu CH P(0CH CH u IM-CH2-P(OCH2CH3)2 oo H N u 3 9 xlrr tocn rcn uu n-un cu M001 3 7 NH-CR2-P(0H3)2 2. 5.0 XIVnoca ua-f T an cn New 9 NH-CHZ-V (04:11

N 9. m8 6.1 xv mac" ran- NH cn Maur NH-CHZOH consumed, the treated fiberself-extinguished upon rewherein R is independently selected from thegroup moval. consisting of OH and EXAMPLE XIX Thirty parts oftris-Ndimethylphosphonomethyl melamine was dry blended with 70 parts ofnylon for about 5 minutes. The mixture was then brought to a melt, mixedthoroughly for about 15 minutes, and then cooled to room temperature.After cooling the mixture was cut into small pieces which were addedcontinuously to a 9 mm diameter glass tube immersed in a hot salt bath(above the melt temperature of the plastic composition). Addition wascontinued until a depth of 9 i plastlc of about 2 mmhad been reached At3. A process of rendering thermoplastic resin compothls a metal wlth awelght attached was put 15 sitions flame retardant which comprisesapplying to and wherein R is lower alkyl.

2. The process of claim 1 wherein said textile is selected from thegroup consisting of cellulosic fibers, proteinoceous fibers and blendsthereof.

into the opening in the glass rod and the rod allowed to Said resinabout 5 to about 50 percent by weight of a cool to room temperature. Thecooled plastic composition was then removed from the glass and tested byCompound of the formula ASTM tests D2863-70 and D635-68. 0 The resultsof these tests are set forth in Table Ill. N

EXAMPLE XX-XXXI 2 "f l- 2 2 Using the same procedure as Example XIX,various additions are mixed with various resin compounds and tested byASTM test method D2863-70 and D635-68. NHCHZR The components, additionsand test results are tabulated in Table III.

TABLE III Percent Flammabil .y Test in Example Plastic Additive Additive0.535

0 0 II N I XIX Nylon (CH3O)2P-CH2HN(/ flmncu -flocufi 26.8 MB N\ N oNHCH P (OCH XX Polyethylene ditto 30 N5 Terephthalate XXI Polypropyleneditto +0 2M7 XXII Epoxy ditto 40 26.0

n 9. mm ABS OH-CHflN-f/ FM-ICH2-P(OCHB)Z "0 SE uncn -on XXIV Polystyreneditto 30 7 SE XXV Polyethylene ditto 30 29.2 NB

Terephthalate XXVI Polypropylene 17. 4 XXVI! Polystyrene 18.0 xxvm A85i9.n xiux Nylon 22.1 XXX Polyethylene 22.7

Terepntholate XXX! Epoxy 22.5

We claim: wherein R is independently selected from the group 1. Aprocess for rendering textiles flame retardant consisting of -OH andwhich comprises applying to said textile, in an amount 60 of from about5 to about 40 percent by weight, a com- (W0) 2 pound of the formula NNHcllzpwk' (,5 and wherein R is lower alkyl.

N l 4, process for rendering thermosetting resin compositlons flameretardant which comprises applying to N R said resin about 5 to aboutpercent by weight of a compound of the formula I NHCH NHCl-l R 2 2 l 8.The article of claim 5 wherein the compound is of wherein R isindependently selected from the group the ula:

consisting of OH and 0 II 9 NHCH -P(0CH CH N o I II and wherein R islower alkyl. HQCH HN I l NHCH P OCH c H 5. An article comprising atextile selected from the 2 N 2 2 3 )2 group consisting of cellulosicfibers, proteinaceous fihers and blends thereof and about 5 to about 50P 9. The article of claim 5 wherein the compound is of cent by weight ofa compound of the formula the formua]:

O O O II N u N (H CO)PCH NH NHCH P(0CH 3 2 2 2 RCHZHN *{4 T uncn pwn 2 fF 3 N 0 i 3O NHCHZR NHCH2P(OCH3)2 10. The article of claim 5 wherein thecompound is wherein R is independently selected from the group 0f theformula! consisting of OH and 0 N H ll HOCH HN NHCH p o R'o 2 2 ,F 2 (CHand wherein R is lower alkyl.

6. An article comprising a resin compound and a HCH -P(0CH flameretardant amount of a compound of the formula 11. The article of claim 5wherein the compound is of the formula:

N ll

wherein R is independently selected from the group 12. The article ofclaim 6 wherein the compound is consisting of OH and of the formula:

N O Q n HO CH NH (R'O) p 2 NHCH -P(OCH and wherein R is lower alkyl. Y

7. The article of claim 5 wherein the compound is of C the formula:

13. The article of claim 6 wherein the compound is of the formula:

0 i N ll HOCHZHN N} NHCHZ-P (0CH2CH3 14. The article of claim 6 whereinthe compound is of the formual:

15. The article of claim 6 wherein the compound is of the formula:

N u HOCHZHN NHCH2-P(0CH3 10 NHCH --P(OCH 16. The article of claim 6wherein the compound is of the formula:

U 0 n N 1| 0 H H c c 3 )ZPCHZNH f T NH CH2P (ocH cH Ni N E)! NH-CH -HOCHCH v UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO.3,885,912

DATED May 27, 1975 INVENTOR(S) Peter Golborn and James J. Duffy Itiscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 4, line 51, "invention with" should read -invention productwith-;

Column 5, line 40, "hexane" should read ---hexene; line 49,"idenecoumarone" should read -indenecoumarone-. Column 6, line 65, "ratewhich" should read -rate at which---. Column 7, line 16, "attempt"should read -attempts. Column 8, line 39, "trimethylomelamine" shouldread --trimethylolmelamine. Column 9, line 19, "16.2%" should read-;--l6.l'%--; line 23, "more cycles" should read more wash .cyclesColumn 10, line 3, "phosphoneomethyl" should read --phosphonomethyl--.Column 11, line 34, "AATC" should read -AATCC-. Claim 2, line 12,"proteinoceous" should read -proteinaceous-.

' Claim 14, line 15, "formual" should read --formula'--. Column 14,lines 5 and 63 and Column 15, lines 15 and 37 and 63 the formula shouldread 0 I (R O) P Signed and Scaled this Nineteenth Day of April 1977[SEAL] Attest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner of Patentsand Trademarks UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION-PATENT NO. 3,885,912

DATED May 27, 1975 |NVENTOR(S) Peter Golborn and James J. Duffy It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown b8|0WI O Column 4,line 51, "invention with" should read invention product with-;

Column 5, line 40, "hexane" should read hexene--; line 49,"idenecoumarone" should read indenecoumarone--. Column 6, line 65, "ratewhich" should read rate at which. Column 7, line 16, "attempt" shouldread attempts. Column 8, line 39, "trimethylomelamine" should readtrimethylolmelamine. Column 9, line 19, "16.2%" should read --l6.l'%-;line 23, "more cycles" should read more wash cycles Column 10, line 3,"phosphoneomethyl" should read phosphonomethyl--. Column 11, line 34,"AA'I'C" should read ---AATCC-. Claim 2, line l2,"prot einoceous" shouldread -proteinaceous---.

' Claim 14, line 15, "formual" should read --formula'-. Column 14, lines5 and 63 and Colunm 15, lines 15 and 37 and 63 the formula should read 0I (R O) P I I Signed and Scaled this Nineteenth Of April 1977 [SEAL]Arrest:

RUTH C. MASON C. MARSHALL DANN Arres ing Officer Commissioner of Patentsand Trademarks

1. A PROCESS FOR RENDERING TEXTILES FLAME RETARDANT WHICH COMPRISESAPPLYING TO SAID TEXTILE, IN AN AMOUNT OF FROM ABOUT 5 TO ABOUT 40PERCENT BY WEIGHT, A COMPOUND OF THE FORMULA
 2. The process of claim 1wherein said textile is selected from the group consisting of cellulosicfibers, proteinoceous fibers and blends thereof.
 3. A process ofrendering thermoplastic resin compositions flame retardant whichcomprises applying to said resin about 5 to about 50 percent by weightof a compound of the formula
 4. A process for rendering thermosettingresin compositions flame retardant which comprises applying to saidresin about 5 to about 50 percent by weight of a compound of the formula5. An article comprising a textile selected from the group consisting ofcellulosic fibers, proteinaceous fibers and blends thereof and about 5to about 50 percent by weight of a compound of the formula
 6. An articlecomprising a resin compound and a flame retardant amount of a compoundof the formula
 7. The article of claim 5 wherein the compound is of theformula:
 8. The article of claim 5 wherein the compound is of theformula:
 9. The article of claim 5 wherein the compound is of theformual:
 10. The article of claim 5 wherein the compound is of theformula:
 11. The article of claim 5 wherein the compound is of theformula:
 12. The article of claim 6 wherein the compound is of theformula:
 13. The article of claim 6 wherein the compound is of theformula:
 14. The article of claim 6 wherein the compound is of theformual:
 15. The article of claim 6 wherein the compound is of theformula:
 16. The article of claim 6 wherein the compound is of theformula: